DE3702300A1 - WATER-SOLUBLE, CROSS-LINKABLE POLYCONDENSATES - Google Patents

Description

The invention relates to water-soluble, crosslinkable polycondensates, which are obtained by reacting
A) a reaction product

• 1. s-trichlorotriazine and
• 2. an amine that is a terminal primary or secondary and a terminal quaternary ammonium group contains or from mixtures of the amine with a diamine that is a terminal primary or secondary and a terminal tertiary Amino group contains, in a molar ratio of 100: 1 to 1: 1.

in a ratio of 0.75 to 1.15 moles of amine per mole of s-trichlorotriazine
B) a basic polymer consisting of:

• 1. a polyamide amine with a molecular weight of at least 1000, made from:
  α ) aliphatic polyamines which contain at least two amino groups capable of amide formation and at least one further secondary amino group, and β ) aliphatic or aromatic dicarboxylic acids with 2 to 12 C atoms or their functional derivatives and / or γ ) 3 to 6 C atoms containing amino carboxylic acids or their lactams or
• 2. a polyalkylene polyamine with a molecular weight of at least 2000, of the formula wherein
  R₁, R₂, R₄, R₆, R₈ and R₉ independently of one another are hydrogen or a C₁-C₄-alkyl radical,
  R₃, R₅ and R₇ independently of one another for hydrogen, methyl, ethyl or hydroxy,
  a, b and c independently of one another for an integer from 0 to 4,
  d for 0 or 1 and
  x for an integer from 20 to 2000
  mean,
  or
• 3. one by polymerizing 1,2-alkyleneimines polyalkyleneimine produced

in a molar ratio of 0.75 to 1.15 mol of base nitrogen of components B) per mol of intermediate A)
are available
their production and their use as paper auxiliaries to increase wet tear strength, retention and to accelerate drainage during paper production, and as aftertreatment agents for colored textile material.

The crosslinkable polymers according to the invention contain per mole of s-trichlorotriazine used 0.1 to 0.9 moles of reactive chlorine atoms. It will be smaller amounts of reactive chlorine atoms than theoretically found possible because a Hydrolysis occurs as a side reaction.

In German patent application 34 00 052 and in US Pat. No. 3,446,284 discloses water-soluble, halogen-containing polymers described by Implementation of s-trichlorotriazine with a cationic Amine containing groups and further reaction with a basic dicyandiamide resin can be obtained. The polymers are used as textile auxiliaries for improvement the wet fastness of dyed textile material. In contrast to these condensates much higher according to the present invention Achieve molecular weights.

In the German Offenlegungsschrift 26 26 495 reactive triazine systems with cationic amine structures described the anionic affinity Dyes on natural or synthetic fiber materials increase.

Preferred ammonium compounds or diamines A) 2 are that of the formulas

and

respectively.

and

wherein
R₁ represents hydrogen or a C₁-C₄ alkyl radical,
R₁₀, R₁₁ and R₁₂ independently of one another are methyl or ethyl,
W for phenylene or cyclohexylene,
n for an integer from 2 to 6,
p for an integer from 1 to 3 and
A ^{⊖ represents} an anion, especially halide, sulfate or methyl sulfate.

0.9 to 1.1 moles of amine per mole of s-trichlorotriazine are preferred used.

The diamines V and VI are preferably in Mixture with the ammonium compounds II or III used, the molar mixing ratios II: V or III: VI 100: 1 to 1: 1, preferably 100: 1 to 3: 1, be.

The basic polymers B) preferably consist of

• 1. a polyamide amine with a molecular weight of 2000 to 30,000, made from α ) aliphatic polyamines of the formula in whichR₁₃ and R₁₄ are independently hydrogen or methyl a and b are an integer from 0 to 4 and t and v are an integer from 1 to 5, and β ) aliphatic or aromatic dicarboxylic acids having 4 to 10 carbon atoms or their esters, anhydrides, half-esters or amides, and / or γ ) amino carboxylic acids containing 3 to 6 carbon atoms or their lactams, or
• 2. a polyalkylene polyamine of the formula I with a Molecular weight of at least 5000 or
• 3. one by polymerizing 1,2-ethyleneimine, manufactured product.

The crosslinkable polycondensates are used in particular in Molar ratio of 0.85 to 1.1 moles of base nitrogen Component B per mole of precursor A.

Preferred polycondensates according to the invention are those obtained by reacting
A) a reaction product

• 1. s-trichlorotriazine and
• 2. 1-amino-3 (trimethylammonium) propane methyl sulfate or a mixture of 1-amino-3- (trimethylammonium) propane methyl sulfate and 1-methylamino-3-dimethylamino-propane in the ratio 100: 1 to 3: 1

in the ratio of 0.9 to 1.1 moles of amine per mole of s-trichlorotriazine, with
B) a basic polymer consisting of:

• 1. a polyamide amine with an average molecular weight from 3000 to 15,000 from diethylenetriamine and adipic acid, or
• 2. a polyalkylene polyamine with an average molecular weight of 20,000 to 150,000 produced by condensation of
  1,2-dichloroethane with
  1,6-diaminohexane, dipropylenetriamine, methyl bis (3-aminopropyl) amine or diethylenetriamine in a ratio of 0.85 to 1.1 moles of base nitrogen from component B) per mole of A)

are available.

The crosslinkable polycondensates according to the invention contain per mole of s-trichlorotriazine used preferably 0.2 to 0.8 mol of reactive chlorine atoms.

They are preferably water-soluble and not gel-like. The aqueous solutions have a solids content from 5 to 40% by weight, preferably 10 to 30% by weight, a Viscosity from 5 to 300 mPas, preferably 10 to 200 mPas.

To produce intermediate A, this is placed in water or aqueous-organic medium suspended s-trichlorotriazine and specifies at temperatures from 0 to 20 ° C, preferably 2 to 10 ° C, per mole of s-trichlorotriazine 0.75 to 1.15 mol, preferably 0.9 to 1.1 mol, of one Diamine or diamine mixture. Then stir 30 minutes to 4 hours, preferably 1 to 2 hours at the above temperature, the resulting product goes into solution.  

Both during the addition of the amine and when stirring the resulting acid is removed using a KOH, Neutralize NaOH or soda solution and adjust the pH from 5 to 7.5, preferably 5.5 to 7.

After the removal of small insoluble components the preliminary product A with the basic polymer B implemented. An intermediate insulation of A is not necessary.

To react with polymer B, it is dripped as 15 to 60%, preferably 20 to 40%, aqueous Solution at 10 to 60 ° C, preferably 15 to 40 ° C, to the submitted preliminary product A and then stirred as long until a sample of the reaction mixture as 20% Solution at 25 ° C a viscosity of at least 5, preferably 10 to 200 mPas.

The pH value is also adjusted with the help of an appropriate KOH, NaOH or soda solution at 5 to 8.5, preferably 6 to 7.5. To end the Condensation reaction is added to the reaction mixture an organic or inorganic acid, such as formic acid, Acetic acid, lactic acid, citric acid, tartaric acid, Oxalic acid, malonic acid, succinic acid, glutaric acid, Maleic acid, hydrochloric acid, phosphoric acid or sulfuric acid to, so that the pH at 1 to 6.5, preferably 2.5 to 6.

There are storage-stable, clear aqueous solutions with receive reactive groups that have networking, e.g. B.  to water-insoluble films, allow and reactions with on a textile substrate or paper.

Suitable diamines (II) and (III) are compounds such as they are described in DE-A-26 26 495, pages 23 and 24 will.

In particular, the following should be mentioned:
1-amino-2- (trimethylammonium) ethane chloride, 1-amino-3- (trimethylammonium) propane methyl sulfate, 4-amino-benzyltrimethylammonium methyl sulfate.

The following may be mentioned as diamines (V) and (VI):
1-amino-3-dimethylamino-propane, 1-methylamino-3-dimethylamino-propane and 4-amino-benzyldimethylamine.

Mixtures of these compounds can also be used will.

The following may be mentioned as aliphatic polyamines (VII):
Diethylene triamine, triethylene tetramine, tetraethylene pentamine, pentaethylene hexamine, hexaethylene heptamine, dipropylene triamine, tripropylene tetramine and dihexamethylene triamine.

Preferred dicarboxylic acids B 1. β ) are succinic acid, glutaric acid, adipic acid, sebacic acid, terephthalic acid, isophthalic acid and itaconic acid.

Preferred compound B 1. γ ) is ε- caprolactam.

The polyalkylene polyamines of the formula (I) can by Implementation of

Alkylene polyamines with two primary and optionally secondary or tertiary amino groups, for example 1,2-diaminoethane, 1,3-diaminopropane, 1,4-diaminobutane, 1,6-diaminohexane, diethylenetriamine, dipropylenetriamine, Dihexamethylene triamine, methyl bis (3-aminopropyl) amine and ethyl bis (3-aminopropyl) amine,

with compounds that are bifunctional to these amines, especially dihaloalkanes through an OH group may be substituted, and epihalohydrins, for example 1,2-dichloroethane, 1,2-dibromoethane, 1-chloro-2-bromo-ethane, 1,2-dichloropropane, 1,3-dichloropropane, 1-chloro-3-bromopropane, 1,4-dichlorobutane, 1,5-dichloropentane, 1,6-dichlorohexane, 1,3-dichloro-2-hydroxypropane and epichlorohydrin,

getting produced.

Preferred reaction products of the formula (I) are derived from 1,6-diaminohexane, dipropylenetriamine, methyl bis (3-aminopropyl) amine or diethylene triamine and dichloroethane produced.

The water-soluble, crosslinkable according to the invention Polycondensates are used as paper aids  to increase wet tensile strength, to improve retention and drainage acceleration.

For this purpose, they are miscible with water in every ratio Products in diluted form before the paper stock added to the sheet formation or before the headbox, the dosing point is chosen so that a good Distribution of the aid in the raw material suspension is secured. Based on the dry weight of the Paper is usually 0.1 to 0.8 wt .-% of Polycondensates used. The new tools can used by everyone in paper manufacturing Raw materials, e.g. B. for bleached and unbleached Pulp, wood pulp, waste paper, etc. are used will.

The crosslinkable polycondensates are also suitable to improve wet and wash fastness (up to 40 ° C) of textile material dyed with anionic dyes. Here are natural fibers, such as cotton, Wool or blended fabric made of it with synthetic fibers, such as polyamide, polyacrylonitrile or cellulose esters call.

The new tools are preferred after Dyeing or printing the textile materials in the pull-out process for fleet ratios from 1: 5 to 1: 50 or in a continuous process on the foulard brought.  

The amount used of the substances according to the invention the foulard is 2.0 to 50 g (100% product), preferred 5.0 to 20 g (100% product) per liter of padding liquor (Fleet intake 100%). during the pull-out process will be 0.2 to 5.0% (100% goods), based on the Dry weight of the textile used.

The aftertreatment is carried out at temperatures from 15 to 100 ° C, advantageously 20 to 60 ° C, and a pH of 6 to 11, preferably 7 to 10, carried out.

example 1

• a) 95 ml of dimethyl sulfate are added to a solution of 102 g of 1-amino-3-dimethylaminopropane in 300 ml of toluene at 3 to 7 ° C. in 1 hour, and the mixture is stirred at 10 ° C. for 30 minutes and at 25 ° C. for 1 hour.
  The toluene phase is then separated off, concentrated and dried at 50 ° C. in vacuo. 197 g of a clear, slightly yellowish oil which slowly crystallizes out are obtained.
  NMR investigations show that the desired alkylation takes place with 70 to 80% selectivity.
• b) 25.0 g of the compound described in Example 1a), dissolved in 50, are added to 18.5 g (0.1 mol) of s-trichlorotriazine in 100 ml of water / 25 g of ice at 5 ° C. with cooling in 30 minutes ml of water. With the aid of a 2N NaOH solution, the pH is kept at 5.2 to 5.4 by trapping the acid that forms.
  After undissolved constituents have been filtered off (0.5 g), the mixture is warmed to 16 ° C. and 39.4 g of a 50% strength aqueous solution of a polyamide amine of DE-B-19 06 450 are added in 30 minutes at pH 6.7. Column 6, lines 16 to 36, mixed with 39.4 ml of water. The mixture is stirred at 25 ° C. and pH 7.0 for 2 1/2 hours, the viscosity increasing, and the pH is then adjusted to 5 with formic acid. Viscosity: 10 mPas organically bound chlorine: 0.054 mol solids content: 15.5%.

Example 2

To 46.3 g (0.25 mol) s-trichlorotriazine in 50 ml water / 50 g Ice is dropped at 1 to 5 ° C in 50 minutes with vigorous cooling, 49.0 g (0.28 mol) of 1-amino-2- (trimethylammonium) ethane chloride, dissolved in 50 ml Water and 110 ml of 2N NaOH.

The mixture is then stirred at 10 ° C. for 1 hour. The pH during the addition and stirring with a 2N NaOH solution kept at 6.

Undissolved portions (1.8 g) are filtered off and heated to 20 ° C and drips 102 g at pH 7.0 in 30 minutes 50% aqueous solution of a polyamide amine DE-B-19 06 450, column 6, lines 16 to 36, in a mixture with 102 ml of water.

Then stirred for 2 1/2 hours at pH 7.0 and 20 to 22 ° C. This increases the viscosity of the condensate. Now the pH is adjusted to 4.5 with formic acid.

Viscosity: 17 mPas Solids content: 20.3% organically bound chlorine 0.11 mol  

Example 3

• a) 53.0 g of 1-amino-3-dimethylamino-propane are in 200 ml of water dissolved and at 0 to 5 ° C inside added in 90 minutes with 56.9 ml of dimethyl sulfate. Then 30 minutes at 0 ° C and 1 hour stirred at 25 ° C.
• b) 164 g of a solution according to Example 3a) are added dropwise to 46.3 g (0.25 mol) of s-trichlorotriazine in 50 ml of water / 50 g of ice at 0 to 5.degree. C. and the mixture is stirred at 5 for 1 hour ° C after. The pH is kept at 6 during the entire reaction time with the aid of a 10% NaOH solution.
  It is filtered off (<1 g), heated to 20 ° C. and 103 g of a 50% strength aqueous solution of a polyamide amine from DE-B-19 06 450, column 6 are added at pH 6.5 to 7.0 in 45 minutes , Lines 16 to 36, in a mixture with 103 ml of water.
  Now the mixture is stirred for a further 20 minutes at 20 ° C. and pH 7, the viscosity increasing. The pH is adjusted to 2.5 using a hydrochloric acid solution. Viscosity: 30 mPas (25 ° C) Solids content: 23.5% organically bound chlorine: 0.19 mol.

Example 4

• a) 86.7 g of 1-amino-3-dimethylamino-propane are added 0 to 5 ° C in 300 ml of water and this Temperature with cooling with 80.7 ml of dimethyl sulfate transferred. Then 30 minutes at 5 ° C and 1 hour stirred at 25 ° C.
• b) 725 g of methyl bis (3-aminopropyl) amine and 1490 ml of water before, then at 120 ° C in the pressure reactor 500 g of 1,2-dichloroethane in 1 hour and keep stirring for 90 minutes. Then you drip Add 2150 ml of water, aerated and degassed. Viscosity: 85 mPas (25 ° C) Solids content: 25.0% by weight.
• c) 162.7 g of a solution according to Example 4a) are added to a dispersion of 46.3 g (0.25 mol) of s-trichlorotriazine in 50 ml of water / 50 g of ice at 0 to 5 ° C. in the course of 1 hour and the mixture is stirred 1 hour at 5 ° C. The pH is maintained at 6 with a 10% NaOH solution throughout the reaction.
  Subsequently, undissolved constituents are filtered off (<1.0 g) and 250 g of a 25% strength aqueous solution according to Example 4b) are added in a mixture with 150 ml of water at pH 6.5 to 7.5 in 45 minutes. The temperature during the addition is 15 to 20 ° C.
  The mixture is then stirred for a further 40 minutes at pH 7.5 and 30 ° C. The viscosity increases noticeably. The pH is adjusted to 4.0 using a phosphoric acid solution. Viscosity: 64 mPas (25 ° C) Solids content: 20.2% by weight of organically bound chlorine: 0.11 mol.

Example 5

• a) 11.2 g of 1-amino-3-dimethylamino-propane are added 0 to 5 ° C in 50 ml of water and this Temperature mixed with 10.2 ml of dimethyl sulfate. Then 1 hour at 5 ° C and 1 hour at 25 ° C. touched.
• b) A solution according to Example 5a is added to a dispersion of 18.5 g (0.1 mol) of s-trichlorotriazine in 40 ml of water / 20 g of ice at 2 ° C. in 45 minutes and the mixture is stirred for 90 minutes. During the entire reaction, the pH is kept at 5.8 to 6.0 with a 2N NaOH solution.
  After filtering off insoluble constituents (0.2 g), 106 g of a 25% strength polyalkylene polyamine according to Example 4b) are added at 25 to 30 ° C. in a mixture with 50 ml of water.
  The mixture is then stirred at 20 ° C for 20 minutes and then adjusted to pH 4.0 with a formic acid solution. Viscosity: 43 mPas (25 ° C) Solids content: 18.7% by weight of organically bound chlorine: 0.04 mol.

Example 6

• a) 41.0 g of 1-amino-3-dimethylamino-propane are added 0 to 5 ° C in 80 ml of water / 40 g of ice and at this temperature with 38 ml of dimethyl sulfate transferred. Then 30 minutes at 5 ° C, 30 minutes stirred at 20 ° C and 30 minutes at 45 ° C.
• b) To a dispersion of 74 g (0.4 mol) of s-trichlorotriazine in 200 ml of water / 100 g of ice / 10 g of Na₂SO₄, a solution according to Example 6a) is added at 0 to 5 ° C. in 35 minutes and the mixture is stirred for 2 hours at 10 ° C. During the entire reaction, the pH is kept at 5.5 to 6.0 using a 2N KOH solution.
  After insoluble parts have been filtered off (4.7 g), 300 g of a 20% strength polyalkylene polyamine according to DE-A-28 33 654, example pages 7 and 8, are added in a mixture with 100 ml at 75 to 20 ° C. in 75 minutes Water too. The mixture is then stirred at 25 ° C. for 15 minutes and adjusted to pH 3.8 with a sulfuric acid solution. Viscosity: 35 mPas (25 ° C) Solids content: 20.4% by weight of organically bound chlorine: 0.13 mol.

Example 7

115 ml of a solution are added at 5 to 10 ° C. in 30 minutes according to Example 6a) to 37.0 g (0.2 mol) of s-triazine in 100 ml of water / 50 g of ice and stirred for 2 hours at 10 ° C to. During the entire implementation, the pH kept at 5.5 to 7.0 g by means of a soda solution.

Undissolved constituents are now filtered off (1.7 g). 110 g of one are added at 15 to 20 ° C. in 80 minutes 25% solution of a polyalkylene polyamine according to De-A-23 51 754, Example page 4, with an average molecular weight from 20,000 to 150,000 mixed with 75 ml Water too.

The mixture is then stirred at 30 ° C. for 20 minutes and then added Using a sulfuric acid solution to pH 3.5.

Viscosity: 13 mPas (25 ° C) Solids content: 18.7% by weight organically bound chlorine: 0.05 mol.

A smeared film of the product was 4 hours dried at 100 ° C. This creates a very cloudy, brittle film that is insoluble in water.  

Example 8

Woolen yarns equipped with Hercosett S 7 "Superwash" and with a dye of DE-A-24 04 314, Example 54, were colored with at 50 ° C for 30 minutes aftertreated a liquor, the liter 5.0 g of the reaction product contains according to Example 1b) and with soda is adjusted to pH 9.0 to 9.5. Then it is rinsed acidified with acetic acid and dried. The authenticity checks of the post-treated dyeings reach without negative influence on rub fastness a clearly higher level than untreated stains.

Claims (13)

1. Crosslinkable polycondensates, which are produced by the implementation of
A) a reaction product

• 1. s-trichlorotriazine and
• 2. an amine which contains a terminal primary or secondary and a terminal quaternary ammonium group or from mixtures of the amine with a diamine which contains a terminal primary or secondary and a terminal tertiary amino group in a molar ratio of 100: 1 to 1: 1.

in a ratio of 0.75 to 1.15 moles of amine per mole of s-trichlorotriazine
B) a basic polymer consisting of:

• 1. a polyamide amine with a molecular weight of at least 1000, made from: α ) aliphatic polyamines which contain at least two amino groups capable of amide formation and at least one further secondary amino group and β ) aliphatic or aromatic dicarboxylic acids with 2 to 12 carbon atoms or their functional derivatives and / or q ) 3 to 6 C-containing aminocarboxylic acids or their lactams or
• 2. a polyalkylene polyamine with a molecular weight of at least 2000, of the formula wherein
  R₁, R₂, R₄, R₆, R₈ and R₉ independently of one another are hydrogen or a C₁-C₄-alkyl radical,
  R₃, R₅ and R₇ independently of one another for hydrogen, methyl, ethyl or hydroxy,
  a, b and c independently of one another for an integer from 0 to 4,
  d for 0 or 1 and
  x for an integer from 20 to 2000
  mean or
• 3. a polyalkyleneimine prepared by polymerizing 1,2-alkyleneimines in a molar ratio of 0.75 to 1.15 mol of base nitrogen of components B) per mol of intermediate A)

are available. 2. Crosslinkable polycondensates according to claim 1, whose component A is a reaction product

• 1. s-trichlorotriazine and
• 2. an amine of the formulas or and if necessary or wherein
  R₁ represents hydrogen or a C₁-C₄ alkyl radical,
  R₁₀, R₁₁ and R₁₂ independently of one another are methyl or ethyl,
  W for phenylene or cyclohexylene,
  n for an integer from 2 to 6,
  p for an integer from 1 to 3 and
  A ^{⊖ stand} for an anion,

in a molar ratio of 0.9 to 1.1 mol, amine per mol of s-trichlorotriazine, corresponds. 3. Crosslinkable polycondensates according to claim 1, whose component B consists of

• 1. a polyamide amine with a molecular weight of 2000 to 30,000, made from a ) aliphatic polyamines of the formula in the
  R₁₃ and R₁₄ independently of one another for hydrogen or methyl
  a and b for an integer from 0 to 4 and
  t and v stand for an integer from 1 to 5, and b ) aliphatic or aromatic dicarboxylic acid with 4 to 10 C atoms or their esters, anhydrides, half esters or amides, and / or γ ) 3 to 6 C atom-containing aminocarboxylic acids or their lactams, or
• 2. a polyalkylene polyamine according to claim 1 (B, 2) with a molecular weight of at least 5000 or
• 3. a polyethyleneimine obtained by polymerizing 1,2-ethyleneimine

corresponds. 4. Crosslinkable polycondensates according to claim 1, which by Implementation of 0.85 to 1.1 moles of base nitrogen Component B available per mole of component A. are. 5. Crosslinkable polycondensates according to claim 1, which by reacting
A) a reaction product

• 1. s-trichlorotriazine and
• 2. 1-amino-3- (trimethylammonium) propane methyl sulfate or a mixture of 1-amino-3- (trimethylammonium) propane methyl sulfate and 1-methylamino-3-dimethylamino-propane in a ratio of 100: 1 to 3: 1

in a molar ratio of 0.9 to 1.1 mol of amine per mol of s-trichlorotriazine, with
B) a basic polymer consisting of:

• 1. a polyamine with an average molecular weight of 3000 to 15,000 from diethylenetriamine and adipic acid,
• 2. a polyalkylene polyamine with an average molecular weight of 20,000 to 150,000 produced by condensation of α ) 1,2-dichloroethane with β ) diethylenetriamine, dipropylenetriamine, methyl bis (3-aminopropyl) amine or 1,6-diaminohexane in a molar ratio from 0.85 to 1.1 moles of base nitrogen of component B) per mole of A)

are available. 6. Crosslinkable polycondensates according to claim 1, the 5th up to 40% by weight aqueous solutions have a viscosity of Have 5 to 300 mPas. 7. Application of the crosslinkable polycondensates of the claim 1 as paper aid and as post-treatment agent of dyed textile material.